WO2008078052A2 - Procédé de préparation d'un film organique à la surface d'un support solide dans des conditions non-électrochimiques, support solide ainsi obtenu et kit de préparation - Google Patents

Procédé de préparation d'un film organique à la surface d'un support solide dans des conditions non-électrochimiques, support solide ainsi obtenu et kit de préparation Download PDF

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Publication number
WO2008078052A2
WO2008078052A2 PCT/FR2007/052556 FR2007052556W WO2008078052A2 WO 2008078052 A2 WO2008078052 A2 WO 2008078052A2 FR 2007052556 W FR2007052556 W FR 2007052556W WO 2008078052 A2 WO2008078052 A2 WO 2008078052A2
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WIPO (PCT)
Prior art keywords
film
solution
adhesion primer
organic film
preparation
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PCT/FR2007/052556
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English (en)
French (fr)
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WO2008078052A3 (fr
Inventor
Vincent Mevellec
Sébastien ROUSSEL
Serge Palacin
Thomas Berthelot
Cécile Baudin
Adhitya Trenggono
Guy Deniau
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Commissariat A L'energie Atomique
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Publication date
Priority claimed from FR0655653A external-priority patent/FR2910006B1/fr
Priority claimed from FR0754278A external-priority patent/FR2910007B1/fr
Priority claimed from FR0755356A external-priority patent/FR2910008B1/fr
Priority claimed from FR0755659A external-priority patent/FR2910009B1/fr
Priority to AT07871969T priority Critical patent/ATE509977T1/de
Priority to AU2007337938A priority patent/AU2007337938B2/en
Priority to CN2007800504618A priority patent/CN101595170B/zh
Application filed by Commissariat A L'energie Atomique filed Critical Commissariat A L'energie Atomique
Priority to EP07871969A priority patent/EP2121814B1/fr
Priority to JP2009542154A priority patent/JP5588682B2/ja
Publication of WO2008078052A2 publication Critical patent/WO2008078052A2/fr
Publication of WO2008078052A3 publication Critical patent/WO2008078052A3/fr
Priority to IL199417A priority patent/IL199417A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/04—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H10K71/125—Deposition of organic active material using liquid deposition, e.g. spin coating using electrolytic deposition e.g. in-situ electropolymerisation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/701—Langmuir Blodgett films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]

Definitions

  • the present invention relates to the field of organic surface coatings, said coatings being in the form of organic films. It is more particularly related to the use of suitably selected solutions in order to allow the simple and reproducible formation of organic films by coating on conductive or non-conductive surfaces of electricity without going through conventional techniques of surface functionalization.
  • the present invention also relates to a process for the preparation of such organic coatings.
  • Cataphoresis is a technique also used for the coating of conductive surfaces with organic films.
  • Cataphoresis, or cationic electrodeposition process is used to coat metal parts with charged polymers and to provide uniform films on conductive surfaces. This method does not apply to non-conductive parts and can only be carried out using charged polymers already synthesized beforehand. There is no film growth when using cataphoresis but only the deposit of these on the surface.
  • the treatment requires that the parts are in direct contact with the cathode and a very strict control of the parameters of the cathode bath that must be respected.
  • the electrodeposited layer is insoluble but without physical or chemical resistance and therefore requires an additional step of steaming to acquire all these properties. This technique, however, remains poorly suited to small-sized pieces of complex geometry.
  • Self-assembly of monolayers is a very simple technique to implement (Ulman A., "An introduction to ultrathin organic films from Langmuir-Blodgett films to self-assembly", 1991, Boston, Academy Press).
  • This technique requires the use of generally molecular precursors having sufficient affinity for the surface of interest to be coated. This will be referred to as a precursor-surface pair, such as sulfur compounds having an affinity for gold or silver, tri-halo silanes for oxides such as silica or alumina, polyaromatics for graphite or nanotubes. carbon.
  • the formation of the film is based on a specific chemical reaction between a portion of the molecular precursor (the sulfur atom in the case of thiols, for example) and certain "receptor" sites on the surface.
  • a chemisorption reaction ensures the attachment.
  • films of molecular thickness (less than 10 nm) are obtained.
  • couples involving oxide surfaces give rise to the formation of very strongly grafted films (the Si-O bond involved in the chemisorption of tri-halo silanes on silica is among the most stable in chemistry), it is not nothing when one is interested in metals or semi-conductors without oxide. In these cases, the interface bond between the conductive surface and the monomolecular film is fragile.
  • the self-assembled monolayers of gold thiols desorb as soon as they are heated above 60 ° C., or in the presence of a good solvent at ambient temperature, or as soon as they are brought into contact with a oxidizing or reducing liquid medium.
  • the Si-O-Si bonds are embrittled as soon as they are in aqueous or even wet medium, in particular under the effect of heat.
  • Polymer electrografting is a technique based on electro-active initiation and polymerization, by electro-induced propagation on the surface of interest, acting as an electrode and an initiator. Polymerization (Palacin, S., et al., "Molecule-to-Metal Bonds: Electrografting Polymers in Conductive Surfaces.” Chemphyschem, 2004. 5 (10): 1469-1481).
  • Electrografting requires the use of precursors adapted to its initiation mechanism by reduction and propagation, generally anionic since cathodically initiated electrografting, which is applicable to noble and non noble metals, is often preferred (unlike electrografting by anodic polarization which is only applicable to noble or carbonaceous substrates: graphite, vitreous carbon, boron doped diamond).
  • "Impregnated vinyl” molecules that is to say carriers of electron-withdrawing functional groups, such as acrylonitriles, acrylates, vinylpyridines ... are particularly suitable for this process which gives rise to numerous applications in the field of microelectronics or biomedical.
  • the adhesion of the electrograft films is provided by a covalent carbon-metal bond (G. Deniau et al., “Carbon-to-metal bonds: electroreduction of 2-butenenitrile” Surf Sci., 2006, 600, 675).
  • the polymerization is essential for the formation of the carbon / metal interface bond: it has indeed been shown (G. Deniau et al., "Coupled Chemistry Revisited in the Attempt Cathodic Electropolymerization of 2- Butenenitrile. ", Journal of Electroanalytical Chemistry, 1998, 451, 145-161) that the mechanism of electrografting proceeds by an electro-reduction of the monomer in the immediate vicinity of the surface, to give an unstable anion radical capable of grafting itself with covalently by its radical termination on the electrode. The grafted anion thus obtained, if it were not in the immediate vicinity of polymerizable molecules, desorbed to return to solution (op.cit.).
  • the addition reaction (of Michael addition type) of the charge of the first chemisorbed anion on a free monomer provides a second means of stabilizing the reaction intermediate: the product of this addition again gives a grafted anion, where the charge however "moved" away from the surface, which helps to stabilize the adsorbed edifice.
  • This dimeric anion can itself again be added to a free monomer, and so on, each new addition providing additional stability by relaxation of the charge repulsion / polarized surface, which is to say that the interface link the first, temporary, anion radical becomes stable as the polymerization takes place.
  • electrografting is the only technique that makes it possible to produce grafted films with specific control of the interface link.
  • the only technique for grafting polymer films from activated vinyl monomers onto necessarily conductive surfaces is to electro-initiate the polymerization reaction from the surface via a potentiostat followed by chain growth. , monomer per monomer requiring the use of an electrochemical cell with a cathode and anode as well as application of a voltage across them.
  • Ortiz et al. have described the grafting of diazonium salts synthesized in situ in aqueous acid phase by electrochemical activation ("Electrochemical modification of a carbon electrode using aromatic diazonium salts.” Journal of Electroanalytical Chemistry, 1998.
  • the international application WO 03/018212 describes in particular a method of grafting and growth of a conductive organic film on an electrically conducting surface, the grafting and the growth being carried out simultaneously by electroreduction of a precursor diazonium salt of said film organic.
  • the present invention makes it possible to solve the disadvantages of the processes and coatings of the state of the art and is different from the prior art, especially in that it makes it possible to carry out the grafting of films of polymers or organic copolymers in the absence of of electrical voltage.
  • the proposed method thus makes it possible to graft films onto surfaces of various natures and its application is not limited to conductive or semi-conductive surfaces of electricity.
  • the present invention relates to a process for preparing an organic film on the surface of a solid support, characterized in that it comprises a step of bringing said surface into contact with a liquid solution comprising: at least one solvent,
  • adhesion primer in non-electrochemical conditions and allowing the formation of radical entities from the adhesion primer.
  • organic film is intended to mean any film of organic nature, derived from several units of organic chemical species, covalently bonded to the surface of the support on which the process which is the subject of the present invention is carried out. invention. It is particularly a film covalently bonded to the surface of a support and comprising at least one layer of similar structural units of nature. Depending on the thickness of the film, its cohesion is ensured by the covalent bonds that develop between the different units.
  • reaction solvent may be protic or aprotic in nature. It is preferred that the primer that is employed be soluble in the reaction solvent.
  • protic solvent is meant, in the context of the present invention, a solvent which comprises at least one hydrogen atom capable of being released in the form of a proton.
  • the protic solvent is advantageously chosen from the group consisting of water, deionized water, distilled water, acidified or not, acetic acid, hydroxylated solvents such as methanol and ethanol, and low glycols. molecular weights such as ethylene glycol, and their mixtures.
  • the protic solvent used in the context of the present invention consists only of a protic solvent or a mixture of different protic solvents.
  • the protic solvent or the mixture of protic solvents may be used in admixture with at least one aprotic solvent, it being understood that the resulting mixture has the characteristics of a protic solvent.
  • Acidified water is the preferred protic solvent and, more particularly, acidified distilled water or acidified deionized water.
  • aprotic solvent is meant, in the context of the present invention, a solvent which is not considered as protic. Such solvents are not likely to release a proton or accept one under non-extreme conditions.
  • the aprotic solvent is advantageously chosen from dimethylformamide (DMF), acetone and dimethyl sulfoxide (DMSO).
  • adheresion primer corresponds, in the context of the present invention, to any organic molecule susceptible, under certain conditions, to chemisorber on the surface of a solid support by radical reaction such as radical chemical grafting.
  • Such molecules comprise at least one functional group capable of reacting with a radical and also a reactive function with respect to another radical after chemisorption. These molecules are thus capable of forming a film of polymeric nature after grafting of a first molecule to the surface of a support then reaction with other molecules present in its environment.
  • radical chemical grafting refers in particular to the use of molecular entities having an unpaired electron to form covalent link bonds with a surface of interest, said molecular entities being generated independently of the surface on which they are intended to be grafted.
  • the radical reaction leads to the formation of covalent bonds between the surface concerned and the grafted adhesion primer derivative and then between a grafted derivative and molecules present in its environment.
  • the term "derivative of the adhesion primer” means a chemical unit resulting from the adhesion primer, after the latter has reacted by radical chemical grafting, in particular with the surface of the solid support, or with another radical, implemented in the context of the present invention. It is clear to those skilled in the art that the reactive function with respect to another radical after chemisorption of the adhesion primer derivative is different from the function involved in the covalent bond, especially with the surface of the solid support.
  • the adhesion primer is preferably a cleavable aryl salt selected from the group consisting of aryl diazonium salts, ammonium aryl salts, aryl phosphonium salts and aryl sulfonium salts.
  • the aryl group is an aryl group which may be represented by R as defined below.
  • - R represents an aryl group.
  • aryl group of the cleavable aryl salts and in particular the compounds of formula (I) above mention may advantageously be made of aromatic or heteroaromatic carbonaceous structures, optionally mono- or polysubstituted, consisting of one or more aromatic rings or heteroaromatic compounds each having from 3 to 8 atoms, the heteroatom (s) possibly being N, O, P or S.
  • the substituent (s) may contain one or more heteroatoms, such as N, O, F, Cl, P, Si, Br or S as well as C 1 to C 6 alkyl groups in particular.
  • R is preferably chosen from aryl groups substituted with electron-withdrawing groups such as NO 2 , COH, ketones, CN, CO 2 H, NH 2 , esters and halogens.
  • Particularly preferred aryl groups R are nitrophenyl and phenyl radicals.
  • A may especially be chosen from inorganic anions such as halides such as I ⁇ , Br “ and Cl " , haloborates such as tetrafluoroborate, and organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
  • inorganic anions such as halides such as I ⁇ , Br “ and Cl "
  • haloborates such as tetrafluoroborate
  • organic anions such as alcoholates, carboxylates, perchlorates and sulfonates.
  • adhesion primer is soluble in the solvent used.
  • an adhesion primer is considered soluble in a given solvent if it remains soluble up to a concentration of 0.5 M, ie its solubility is at least 0.5 M in normal temperature and pressure conditions (CNTP).
  • Solubility is defined as the analytical composition of a saturated solution as a function of the proportion of a given solute in a given solvent; it can in particular express itself in molarity. A solvent containing a given concentration of a compound will be considered saturated, when the concentration will be equal to the solubility of the compound in this solvent. Solubility can be finite as infinite. In the latter case, the compound is soluble in any proportion in the solvent.
  • the amount of adhesion primer present in the solution used according to the process according to the invention may vary according to the wishes of the experimenter. This amount is particularly related to the desired organic film thickness and the amount of adhesion primer that it is possible and possible to integrate the film. Thus to obtain a grafted film on the entire surface of the solid support in contact with the solution, it is necessary to employ a minimum amount of adhesion primer that can be estimated by molecular size calculations. According to a particularly advantageous embodiment of the invention, the concentration of adhesion primer in the liquid solution is between 10 ⁇ 6 and 5 M approximately, preferably between 5.10 ⁇ 2 and 10 '1 M.
  • a layer said "hook” is formed when the surface is covered by at least one film of monomolecular thickness derived from the adhesion primer and in particular derived from diazonium.
  • the organic film can thus consist solely of a layer of hooked. It is of course possible to use any means of analysis to control the presence of the layer of hook and determine its thickness, such In particular, means may be infrared spectrometry (IR) or X-ray (XPS) and ultraviolet (UV) photoelectron spectroscopy as a function of the atoms and chemical groups present on the adhesion primer employed.
  • IR infrared spectrometry
  • XPS X-ray
  • UV ultraviolet
  • the pH of the solution is less than 7, typically less than or equal to 3. It is recommended to work at a pH between 0 and 3. If necessary, the pH of the solution can be adjusted to the desired value by means of one or more acidifying agents well known to those skilled in the art, for example using inorganic or organic acids such as hydrochloric acid, sulfuric acid, etc.
  • the adhesion primer can either be introduced in the state in the liquid solution as defined above, or be prepared in situ in the latter.
  • the process according to the present invention comprises a step for preparing the adhesion primer, especially when the latter is an aryl diazonium salt.
  • Such compounds are generally prepared from aryleamine, which may contain several amino substituents, by reaction with NaNU 2 in acidic medium.
  • aryleamine which may contain several amino substituents
  • non-electrochemical conditions in the context of the present invention in the absence of electrical voltage.
  • the non-electrochemical conditions are conditions which allow the formation of radical entities from the adhesion primer, in the absence of the application of any electrical voltage to the surface of the solid support or in the solution liquid. These conditions involve parameters such as, for example, the temperature, the nature of the solvent, the presence of a particular additive in the solution, stirring while the electric current does not occur during the formation of radical entities.
  • the non-electrochemical conditions allowing the formation of radical entities are numerous and this type of reaction is known and studied in detail in the prior art (Rempp & Merrill, Polymer Synthesis, 1991, 65-86, Huthig & Wepf).
  • the thermal environment is a function of the temperature of the solution. Its control is easy with the heating means usually employed by those skilled in the art. Using an environment The thermostat is of particular interest since it allows precise control of the reaction conditions.
  • the kinetic environment essentially corresponds to the agitation within the solution. It is not a question here of the agitation of the molecules in itself (elongation of bonds, etc.), but of the global movement of the molecules within the solution.
  • a vigorous agitation for example using a magnetic bar or ultrasound, allows in particular to bring kinetic energy to the solution and thus destabilize the adhesion primer to form radicals. .
  • non-electrochemical conditions allowing the formation of radical entities are typically selected from the group consisting of thermal, kinetic, chemical, photochemical, radiochemical conditions and combinations thereof.
  • the non-electrochemical conditions allowing the formation of radical entities are chosen from the group consisting of thermal, chemical, photochemical and radiochemical conditions and their combinations with each other and / or with the kinetic conditions. Conditions not electrochemicals are more particularly chemical conditions.
  • thermal initiators the most common of which are peroxides or azo compounds. Under the action of heat, these compounds dissociate into free radicals; in this case the reaction is carried out at a minimum temperature corresponding to that required for the formation of radicals from the initiator.
  • This type of chemical initiator is generally used specifically in a certain temperature range, depending on their kinetics of decomposition; the photochemical or radiochemical initiators which are excited by radiation triggered by irradiation (most often by UV, but also by ⁇ radiation or by electron beams) allow the production of radicals by more or less complex mechanisms.
  • BusSnH and ⁇ 2 belong to photochemical or radiochemical initiators;
  • initiators essentially chemical initiators, this type of initiator acting rapidly and under normal conditions of temperature and pressure on the adhesion primer to enable it to form radicals.
  • Such initiators generally have a redox potential which is lower than the reduction potential of the adhesion primer used in the reaction conditions.
  • it can thus be for example a metal, usually in finely divided form, such as wool (also called more commonly “straw") metal or metal filings, reducer, such as iron, zinc, nickel, a metal salt and particularly in the form of a metallocene, a organic reducer like hypophosphorous acid
  • the liquid solution implemented in the context of the process according to the invention further comprises one or more chemical initiator (s) chosen from:
  • an organic or inorganic base in proportions sufficient for the pH of the liquid solution to be greater than or equal to 4.
  • a previously irradiated polymeric matrix as defined herein.
  • halogenated initiators such as 'iodine, ⁇ -haloalkyls having aryl, allyl, carbonyl or sulphonyl groups, polyhalogenated compounds such as CCl 4 or CHCl 3, the compounds having covalent bonds which are very labile with halogens and generally corresponding to bonds established between a heteroatom, such as N, S or O, and halogen, potassium persulfate (K 2 S 2 Os), azobis (isobutyronitrile), peroxide compounds such as benzoyl peroxide, tert-butyl peroxide, cumyl peroxide, tert-butyl perbenzoate, tert-butyl hydroperoxide, finely divided reducing metals such as iron, zinc, nickel
  • the amount of initiator will be chosen according to the operating conditions employed. Generally, these are amounts of between 5 and 20% by weight of monomers, typically around 10%.
  • the adhesion primer is an aryl diazonium salt
  • iron wool or steel wool it will generally be of the type (degree of fineness) fine (0), extra fine (00) or super fine (000). More particularly, the diameter of the fibers of the wool will be less than or equal to 3.81 ⁇ 10 -2 mm and typically greater than 6.35 ⁇ 10 -3 mm.
  • irradiated matrices in various forms such as membranes.
  • a membrane will have a micrometric thickness, generally between 1 and 100 microns, especially between 5 and 50 microns, and more particularly close to 9 microns.
  • PVDF polyvinylidene fluoride
  • it is possible to use a polyvinylidene fluoride membrane
  • PVDF photoelectron-irradiated electron-irradiated.
  • the irradiation dose is generally between 10 and 200 kGy, more particularly 100 kGy for the PVDF.
  • Such a membrane may for example have dimensions of 1 cm ⁇ 2 cm ⁇ 9 ⁇ m or a total area of about 4.0054 cm 2 .
  • microparticles for example from 1 ⁇ m to 100 ⁇ m in diameter, or else from nanoparticles, generally from 5 nm to
  • the reduction in the diameter of the particles makes it possible to increase the specific contact surface and therefore the amount of radicals at the surface relative to the same mass of irradiated polymeric material in the form of a membrane.
  • the specific contact area of the irradiated matrix available will be much lower than that of the surface of the solid support on which the grafting must be carried out.
  • the irradiation of a polymeric matrix may consist in subjecting said matrix to an electron beam (also called electron irradiation). More particularly, this step may consist of scanning the polymer matrix with an accelerated electron beam, this beam can be emitted by an electron accelerator (for example, a Van de Graaf accelerator, 2.5 MeV).
  • an electron accelerator for example, a Van de Graaf accelerator, 2.5 MeV.
  • the energy deposition is homogeneous, which means that the free radicals created by this irradiation will be evenly distributed on the surface and in the volume of the matrix.
  • the irradiation step of a polymeric matrix may also consist in subjecting said matrix to bombardment with heavy ions.
  • heavy ions means ions whose mass is greater than that of carbon. Generally, these are ions selected from krypton, lead and xenon.
  • the irradiation creates free radicals in the constituent material of the matrix, this creation of free radicals being a consequence of the energy transfer of the irradiation to said material.
  • PVDF polyvinylidene fluoride
  • ⁇ , ⁇ , Y and ⁇ formed by the association, planar or in helix, of chains.
  • the ⁇ and ⁇ phases are the most common.
  • PVDF is a thermoplastic polymer that can be melted and molded.
  • PVDF mainly based on phase a is generally obtained by cooling from the molten state, for example after simple extrusion.
  • PVDF mainly based on ⁇ phase is generally obtained by cold bi-stretching at less than 50 0 C of predominantly phase-based PVDF ⁇ . It is recommended to use PVDF mainly comprising the ⁇ phase because the crystallinity is greater in this case.
  • the specific contact surface of the Polymeric materials with the solution can be advantageously increased by making them micro or nanoporous.
  • the irradiation step can proceed as follows:
  • the chemical revelation consists of bringing the matrix into contact with a reagent able to hydrolyze the latent traces so as to form hollow channels instead of these.
  • the latent traces generated have short chains of polymers formed by splitting existing chains during the passage of the ion in the material during the irradiation.
  • the rate of hydrolysis during the revelation is greater than that of the non-irradiated parts.
  • the reagents capable of revealing the latent traces are a function of the material constituting the matrix.
  • the latent traces can in particular be treated with a strongly basic and oxidizing solution, such as KOH ION solution in the presence of KMnO 4 at 0.25% by weight at a temperature of 65 ° C, when the polymer matrix is, for example, consisting of polyvinylidene fluoride (PVDF), poly (VDF-co-HFP) (vinylidene fluoride-co-hexafluoropropene), poly (VDF-co-TrFE) (vinylidene fluoride-trifluoroethylene fluoride), poly (VDF-co-TrFE-co-ChloroTrFE)
  • PVDF polyvinylidene fluoride
  • VDF-co-HFP vinylene fluoride-co-hexafluoropropene
  • VDF-co-TrFE vinylene fluoride-trifluoroethylene fluor
  • the electron irradiation is carried out to induce the formation of free radicals on the wall of the channels, the implementation being, in this case, similar to that which has been exposed for the irradiation in general.
  • the beam is oriented in a direction normal to the surface of the membrane and the surface thereof is scanned homogeneously.
  • the irradiation dose generally varies from 10 to 200 kGy for subsequent radiografting, it will typically be close to 100 kGy for PVDF.
  • the dose is usually such that it is greater than the gel dose.
  • the latter corresponds to the dose from which the recombinations between radicals are favored resulting in the creation of interchain bonds leading to the formation of a three-dimensional network (or crosslinking) that is to say the formation of a gel.
  • a dose greater than the gel dose makes it possible to induce, at the same time, crosslinking thus making it possible to improve the mechanical properties of the final polymer.
  • a PVDF membrane of 2 cm and thickness of 9 ⁇ m sees its specific contact surface increase from about 4 cm to about 60 cm for the same membrane having 10 10 pores per cm 2 d an average diameter of 10 nm thus allowing a relative number of radicals present at the surface 15 times greater than for the same non-porous membrane.
  • the liquid solution implemented in the context of the present invention may further contain at least one surfactant as described and defined later.
  • the solid support whose surface is treated according to the method of the invention may be all nature. Indeed, it is on the surface of the sample in contact with the solution that will take place the radical grafting reaction.
  • the surface of the solid support to be treated according to the process according to the present invention typically has at least one atom that can be involved in a radical reaction.
  • the solid support can be conductive or non-conductive of electricity.
  • the solid support may have a greater or lesser surface and variable roughness.
  • the method is applicable to samples of nanometric or metric size.
  • the method can be applied to surfaces of nano-objects such as nanoparticles or nanotubes, typically carbon, or to more complex devices.
  • the invention is applicable to a wide variety of surfaces of interest, the composition of which can be selected from a wide variety of materials. Indeed, the method makes use of grafting of purely radical nature, it does not require that the surface has specifically limiting characteristics such as high conductivity.
  • the surface may be organic or inorganic in nature, and may also be of a composite nature and have a non-uniform composition. Any surface having one or more atom (s) or group (s) of atoms that may be involved in a radical addition or substitution reaction, such as CH, carbonyls (ketone, ester, acid, aldehyde) , OH, ethers, amino, halogen, such as F, Cl, Br, is particularly concerned by the present invention.
  • the solid support can have an inorganic surface that can be chosen from conductive materials such as metals, noble metals, oxidized metals, transition metals, metal alloys and for example Ni, Zn, Au, Pt, Ti, l 'steel.
  • the inorganic surface may also be selected from semiconductor materials such as Si, SiC, AsGa, Ga etc. It is also possible to apply the process to solid supports having a non-conductive surface such as non-conductive oxides such as SiC 2, Al 2 O 3 and MgO. More generally, the inorganic surface of the solid support may consist, for example, of an amorphous material, such as a glass generally containing silicates or a ceramic, as well as a crystalline one such as diamond.
  • the solid support may have an organic surface.
  • an organic surface mention may be made of natural polymers such as latex or rubber, or artificial polymers such as polyamide or polyethylene derivatives, and in particular polymers having ⁇ -type bonds, such as polymers bearing ethylenic bonds, groups carbonyls, imine. It is also possible to apply the process to more complex organic surfaces such as surfaces comprising polysaccharides, such as cellulose for wood or paper, artificial or natural fibers, such as cotton or felt, and fluorinated polymers such as polytetrafluoroethylene
  • the solid support and / or the surface of the solid support used in the context of the present invention consist of a material chosen from the group consisting of metals, wood, paper, cotton, felt, silicon, carbon nanotubes, fluoropolymers and diamond.
  • the surface of the solid support on which the organic film is to be formed is equipped with a mask which covers it at least in part and which isolates it from the liquid solution.
  • the mask typically corresponds to a physical entity that is neither grafted to the surface nor covalently bonded to it. It may especially be a solid material or a thin layer of material, typically from a few ⁇ ngstrom to a few microns, generally of organic nature, deposited on the surface.
  • the mask makes it possible to locally "mask” the chemical reactivity of the surface with respect to the radicals generated during the process and thus results in the controlled formation of a film only on the parts of the surface exposed to the solution, the areas of the support surface equipped with the mask being preserved from the formation of the organic film.
  • the surface of the solid support placed in contact with the liquid solution as defined previously thus typically comprises at least one zone covered with a mask. After removal of the mask at the end of operation, the surface that was protected, unlike the one that was not equipped with a mask, does not include graft film.
  • the mask will consist of a thin layer of inorganic or organic material acting as a layer of less cohesion easily removable under mild conditions.
  • a layer of material is considered as such in that it does not require the use of extreme conditions harmful to the grafted film to be eliminated.
  • the mild conditions correspond to a simple chemical washing, generally carried out using a solvent in which the mask is soluble, to an ultrasonic treatment in a solvent in which the mask is soluble or to a rise in temperature. It is of course desirable that the mask is not soluble in the reaction solvent present in the liquid solution used in the context of the grafting reaction. Thus it is recommended to use a mask which has a surface affinity greater than that which it has for the reaction solvent.
  • the material constituting the mask can thus be chosen from a wide range. It will generally be chosen according to the nature of the solid support.
  • the mask is composed of alkylthiols, in particular long-chain alkylthiols, often C15-C20 and typically C18.
  • the mask can react with the radicals generated during the process. In all cases, it is possible to eliminate it to discover the areas of the surface of the solid support protected grafting on which no organic film will be observed
  • Mask deposition techniques are known to those skilled in the art. This may include coating, spraying or immersion.
  • the mask in the form of a thin layer of material, may for example be deposited by direct drawing from a felt (pencil type) impregnated with the selected material.
  • a felt pencil type
  • On glass it is, for example, possible to use, as a mask, a marker such as those proposed in stationery or fat. It is also possible to use the so-called buffer method.
  • This technique is applicable especially in the case of a solid support having a complexing surface for the sulfur atoms, such as a gold surface, in which case the mask will generally be composed of alkylthiols, in particular long-chain alkylthiols (technical say micro-printing - "microcontact printing” in English), often C15-C20 and typically C18. More generally, conventional lithography techniques can be used to form the mask: spin-coating, then insolation through a physical mask or via a mask. beam of light or controllable particles, then revelation.
  • the process for preparing an organic film on the surface of a solid support comprises a step of bringing said surface into contact with a liquid solution comprising at least one solvent,
  • At least one adhesion primer and at least one monomer different from the adhesion primer and radically polymerizable, under non-electrochemical conditions and allowing the formation of radical entities from the adhesion primer.
  • the protic or aprotic solvent in which it is preferable that the monomer be soluble, the support, the possible chemical primers and a possible mask also applies to the embodiment above.
  • the radically polymerizable monomers used in the context of the present invention correspond to the monomers capable of polymerizing under free radical conditions after initiation by a radical chemical entity. Typically, this is of molecules comprising at least one bond of the ethylenic type, ie of ethylenic type molecules.
  • the vinyl monomers in particular the monomers described in patent application FR 05 02516 as well as in patent FR 03 11491, are particularly concerned.
  • the vinyl monomer or monomers are chosen from the following monomers of formula (II):
  • the groups R 1 to R 4 which are identical or different, represent a non-metallic monovalent atom such as a halogen atom, a hydrogen atom or a saturated or unsaturated chemical group, such as an alkyl or aryl group, a group -COOR 5 in which R 5 represents a hydrogen atom or a C 1 -C 12 and preferably C 1 -C 8 alkyl group, a nitrile, a carbonyl, an amine or an amide.
  • a non-metallic monovalent atom such as a halogen atom, a hydrogen atom or a saturated or unsaturated chemical group, such as an alkyl or aryl group, a group -COOR 5 in which R 5 represents a hydrogen atom or a C 1 -C 12 and preferably C 1 -C 8 alkyl group, a nitrile, a carbonyl, an amine or an amide.
  • the compounds of formula (II) above are in particular chosen from the group consisting of vinyl acetate, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, butyl methacrylate and methacrylate.
  • the monomers employed are those which, conversely soluble compounds in any proportion in the solvent in question, are soluble to a certain proportion in the solvent, ie the value of their solubility in this solvent is over .
  • the monomers that can be used in accordance with the process of the invention can thus be chosen from compounds whose solubility in the reaction solvent is finite and more particularly less than 0.1 M, more preferentially between 5.10 -2 and 10 -6 M.
  • Such monomers include, for example, butyl methacrylate whose solubility, measured under normal conditions of temperature and pressure, is approximately 2.5 ⁇ 10 -3 M in water and methyl methacrylate 4.10 -2 According to the invention, and unless otherwise indicated, the normal pressure and temperature conditions (CNTP) correspond to a temperature of 25 ° C and a pressure of 1.10 5 Pa.
  • CNTP normal pressure and temperature conditions
  • the invention is also applicable to a mixture of two, three, four or more monomers chosen from the monomers previously described.
  • the amount of polymerizable monomers in the solution may vary depending on the wishes of the experimenter. This quantity may be greater than the solubility of the monomer in question in the reaction solvent used and may represent for example 18 to 40 times the solubility of said monomer in the solution at a given temperature, generally the ambient temperature or that of reaction. Under these conditions it is advantageous to employ means allowing the dispersion of the monomer molecules in the solution such as a surfactant or ultrasound.
  • a surfactant when the monomer has a solubility of less than 5.10 -2 M.
  • a precise description of the surfactants that can be used in the context of The invention is given in patent applications FR 06 01804 and FR 06 08945 and in the literature (Deniau et al., Chem Mater 2006, 18, 5421-5428) to which the skilled person can refer.
  • a single surfactant or a mixture of several surfactants can be used.
  • the amount of surfactant (s) needed is variable; it must in particular be sufficient to allow the formation of the organic film.
  • the minimum amount of surfactant (s) can be easily determined by sampling solutions of identical composition but variable concentration of surfactant (s).
  • concentration of surfactant (s) is such that the critical micelle concentration (CMC) is reached and that there can thus be formation of micelles.
  • CMC of a surfactant can be determined by methods known to those skilled in the art, for example by surface tension measurements.
  • the surfactant concentration will be between about 0.5 mM and 5 M, preferably between about 0.1 mM and 150 mM.
  • the recommended concentration of surfactant is usually 10 mM.
  • Surfactants are molecules comprising a lipophilic part (apolar) and a hydrophilic part (polar).
  • apolar lipophilic part
  • polar hydrophilic part
  • anionic surfactants whose hydrophilic part is negatively charged; preferably the surfactant will be alkyl or aryl sulfonates, sulfates, phosphates, or sulfosuccinates associated with a counter ion such as an ammonium ion (NH 4 + ), a quaternary ammonium such as tetrabutylammonium, and alkaline cations such as Na +, Li + and K +; ii) cationic surfactants whose hydrophilic part is positively charged; they are preferably chosen from quaternary ammoniums comprising at least one C 4 -C 22 aliphatic chain associated with an anionic counterion chosen in particular from boron derivatives such as tetrafluoroborate or halide ions such as F-, Br-, I - or Cl-; iii) zwitterionic surfactants which are neutral compounds having formal electrical charges of one unit and of opposite sign; they are preferably
  • the charged surfactants can of course carry several charges.
  • anionic surfactants it is possible, for example, to use tetraethylammonium paratoluenesulphonate, sodium dodecyl sulphate, sodium palmitate, sodium stearate, sodium myristate, sodium di (2-ethylhexyl) sulphosuccinate, methylbenzene sulphonate and ethylbenzene sulphonate.
  • cationic surfactants it is possible, for example, to use tetrabutylammonium chloride, tetradecylammonium chloride, tetradecyltrimethylammonium bromide (TTAB), alkylpyridinium halides bearing an aliphatic chain and alkylammonium halides.
  • TTAB tetrabutylammonium chloride
  • tetradecylammonium chloride tetradecylammonium chloride
  • TTAB tetradecyltrimethylammonium bromide
  • amphoteric surfactants it is possible to use disodium lauroamphodiacetate, betaines such as alkylamidopropylbetaine or laurylhydroxysulfobetaine.
  • nonionic surfactants it is possible to use polyethers such as polyethoxylated surfactants such as, for example, polyethylene glycol lauryl ether (POE23 or Brij® 35), polyols (surfactants derived from sugars), in particular glucose alkylates. such as for example glucose hexanate.
  • polyethers such as polyethoxylated surfactants such as, for example, polyethylene glycol lauryl ether (POE23 or Brij® 35), polyols (surfactants derived from sugars), in particular glucose alkylates. such as for example glucose hexanate.
  • anionic surfactants such as sulfonates, quaternary ammoniums and nonionic surfactants such as polyoxyethylenes.
  • the solubility of the monomer proves not to be an obstacle to the realization of the process through the use of technical means, such as vigorous agitation, which can be induced by ultrasound, which allow the formation of a dispersion and / or an emulsion, for the monomer (s) (s) liquid (s).
  • the solution is in the form of a emulsion or dispersion. It is also possible to use another type of solvent and adapt the initiator accordingly.
  • the process according to the present invention comprises a preliminary step during which the polymerizable monomer or the polymerizable monomer mixture is dispersed or emulsified in the presence of at least one surfactant or by the action of ultrasound, before its mixing with the liquid solution comprising at least one protic solvent and at least one adhesion primer.
  • the process is generally carried out under mild and non-destructive conditions either for the surface of the sample on which it is desirable to graft the film, or for the monomer optionally employed. Thus, it is desirable to work under conditions in which the monomer does not degrade.
  • the temperature of the reaction medium is limited by the reaction solvent, which it is preferable to retain liquid.
  • the process is carried out between 0 and 100 0 C and generally under normal conditions of temperature and pressure (CNTP), depending on where the user is located, often at about 25 ° C at a pressure of about 1 atm .
  • the reaction time is flexible. Indeed, the modulation of the exposure time of the surface of the solid support to the solution makes it possible to vary the thickness of the film that is obtained. It is of course possible for the same type of surface to accurately calibrate the operating conditions that the user will consider optimal, the analysis means described in the examples below are particularly suitable for determining in particular the thickness of the film, its composition as well as incidentally the reaction time. It is, e.g., possible to obtain films whose thickness is between 2 nm and 200 nm by varying the reaction time between 1 and 15 minutes, and, to a diazonium salt concentration of 5.10 ⁇ 2 M, or a monomer concentration of 0.9 M and a diazonium salt of 5.10 -2 M.
  • the process according to the invention may comprise the following steps: a) adding at least one monomer to a solution containing at least one adhesion primer different from said monomer in the presence of at least one solvent and optionally at least one chemical initiator, b) placing the solution obtained in step (a) under non-electrochemical conditions allowing the formation of radical entities from the adhesion primer and optionally from the chemical initiator; c) contacting the surface of the solid support with the solution of step (b).
  • the latter may comprise the following steps: a ') bringing the surface of the solid support into contact with a solution containing at least one adhesion primer in the presence of at least one solvent and optionally at least one chemical initiator and at least one monomer, b ') placing the surface of the solid support in contact with the solution of step (a') under non-electrochemical conditions for forming radical entities from the adhesion primer and optionally from the chemical initiator, c ') optionally adding at least one monomer to the solution obtained in step (b').
  • the following three cases can be envisaged: i.
  • the monomers are not present in the solution of step (a ') and are added only in step (c').
  • step (c') the monomer may be added in solution, in particular in the same solvent as that used in step (a') and advantageously in the form of an emulsion or a dispersion performed beforehand using ultrasound or surfactants.
  • the monomers are present in the solution of step (a ') and the process has no step (c'). This case applies in particular when the primer is a diazonium salt and when the monomer is water-soluble.
  • the method according to the first variant is also usable in this case. iii. a part of the monomers are present in the solution of step (a ') and another part of the monomers of identical or different nature is added in step (c').
  • the adhesion primer can be introduced into the solution or solutions as is, or prepared in situ in the latter or the latter.
  • the method according to the present invention comprises an additional step, prior to grafting, of cleaning the surface on which it is desired to form the organic film, in particular by sanding and / or polishing; additional ultrasound treatment with an organic solvent such as ethanol, acetone or dimethylformamide (DMF) is even recommended.
  • an organic solvent such as ethanol, acetone or dimethylformamide (DMF)
  • the organic films obtained according to the processes previously described are thus essentially polymer or copolymer, resulting from several monomeric units of identical or different chemical species and / or primary adhesion.
  • the films obtained by the process of the present invention are "essentially" of the polymer type insofar as the film also incorporates species derived from the adhesion primer and not only monomers present.
  • An organic film in this particular embodiment is thus in particular a film prepared from at least one type of adhesion primer or at least one type of polymerizable monomer, particularly radical, and at least one type of adhesion primer.
  • the organic film in the context of the invention has a sequence in monomeric units in which the first unit consists of a derivative of the adhesion primer, the other units being indifferently derived from the adhesion primers and polymerizable monomers.
  • the thickness of the film is easily controllable according to the method of the present invention, as previously explained.
  • the skilled person will be able to iteratively determine the optimum conditions to obtain a film of varying thickness. It is also useful to refer to the examples which illustrate the invention and show that it is for example possible to produce films whose thickness is between a few nanometers and several hundred nanometers.
  • the previously disclosed method also makes it possible to access supports comprising functionalizable films.
  • These typically correspond to films having at their surface chemical groups capable of reacting with another chemical group, typically outside the film, to form covalent, ionic or hydrogen bonds, a group corresponding to this definition will be named chemical functionalization group (GCF) in the following the presentation.
  • GCF chemical functionalization group
  • Such groups generally correspond to groups comprising at least one covalent bond between a heterotamone and another element corresponding to a carbon, a hydrogen or another heteroatom.
  • the heteroatom (s) are generally chosen from N, O, S, Cl, Br and Si.
  • a functionalizable film may thus comprise a GCF which may in particular be chosen from hydroxyl, thiol, azide, epoxide, azyridine, amine, nitrile, isocyanate, thiocyanate, nitro, amide, halide, carbonyl functions, such as carboxylic acids, aldehydes, ketones, acid halides, esters and activated esters, and among alkenes or alkynes.
  • GCF which may in particular be chosen from hydroxyl, thiol, azide, epoxide, azyridine, amine, nitrile, isocyanate, thiocyanate, nitro, amide, halide, carbonyl functions, such as carboxylic acids, aldehydes, ketones, acid halides, esters and activated esters, and among alkenes or alkynes.
  • a GCF would not be directly accessible to those skilled in the art from the films that it is likely to prepare, it is of course possible to modify the GCFs that the film comprises using one or more simple chemical reactions.
  • a film derived from acrylic acid which comprises as GCF a CO2H function can be modified by reaction with thionyl chloride (SOCI2) to form a film comprising acid chloride for of GCF.
  • SOCI2 thionyl chloride
  • nitro-benzene film having a nitro function as GCF it can be reduced by iron to give a film having an amine as GCF.
  • a polyacrylonitrile film comprising a nitrile group such as GCF makes it possible, for example, after treatment with LiAlH 4 , to access a film comprising an amine such as GCF.
  • a nitrile group such as GCF
  • the skilled person can refer to the international application WO 2004/005410.
  • Access to functionalisable films allows their subsequent functionalization.
  • the process for preparing an organic film on a support can comprise an additional functionalization step, such a step is applicable in particular to functionalizable films.
  • the functionalization can be carried out by contacting the surface of a film, in particular obtained by the process described above, which can be functionalized, and particularly with a GCF of the film, with a graft.
  • the contacting can be done through a solution, called “functionalization solution”, comprising at least one graft.
  • the reaction will notably take place on the surface of the film but also within it, depending on the GCF present, the thickness of the film and the solvent of the solution.
  • the solvent of the solution comprising the graft will preferably be a swelling solvent.
  • a swelling solvent corresponds to a solvent capable of penetrating into the organic film present on the support. Such solvents, when in contact with the film, generally cause the film to swell in a perceptible manner by optical means, vis-à-vis the eye, or by simple optical microscopy.
  • a standard test for determining whether a solvent is particularly suitable for a film is to deposit a drop of solvent on the surface of the film and observe whether the drop is absorbed within the film. It is desirable to use from among a set of solvents tested those for which the absorption is the fastest. The use of such a solvent leads to a deeper graft grafting within the film.
  • a graft corresponds to an organic compound capable of reacting with the functionalizable film and particularly with a GCF that comprises the functionalizable film.
  • the graft may be any type of organic molecule to the extent that it has a group capable of reacting with a GCF that includes the film on the support.
  • the graft may comprise in its structure a group of interest (GI) corresponding to a substructure having one or more property (s) of interest, as well as, optionally, a linking group (LG) corresponding to a structure essentially free of properties of interest.
  • GI group of interest
  • LG linking group
  • the functionalization is via the LG which has a group that can react with the GCF.
  • the graft, and particularly the GI may in particular have a chelating structure, or a biologically active structure.
  • the GI can thus be chosen in particular from cyclodextrins (CD), such as peranhydrocyclodextrin derivatives, calixarenes, such as calix [4] arene, porphyrins, such as tetrakis (4-bezoic acid), 4 ', 4 '', 4 '' '-
  • the GI may also for example be chosen from polysaccharides and polypeptides.
  • the linking group (LG) generally corresponds to a group that does not develop any interaction other than steric nature, hydrophilic or hydrophobic nature or affinity with the GI, and that does not react significantly with it (no detectably). Typically, it may for example be a chain of essentially aliphatic nature, eg alkyl chain, preferably from 1 to 22, and typically 3 to 16, carbon atoms, an aromatic chain, or a chain heterocyclic, such as a polyether chain.
  • the LG advantageously comprises one or more reactive heteroatoms capable of reacting with a GCF.
  • a film comprising grafted molecules and having properties of interest on the surface of a support.
  • Such films may especially correspond to chelating or filtration films or to films having biomolecules.
  • the skilled person can refer to the international application WO 2004/005410 with regard to examples of molecules that can be grafted.
  • the functionalization it is possible to access supports covered with an organic film comprising biomolecules such as proteins, polypeptides, peptides, antibodies and antibody fragments, polysaccharides or oligonucleotides.
  • biomolecules such as proteins, polypeptides, peptides, antibodies and antibody fragments, polysaccharides or oligonucleotides.
  • the graft then corresponds to a derivative of a biomolecule.
  • a support having a film comprising polymethacrylonitrile, obtained using a diazonium and methacrylonitrile it is possible to graft a protein such as avidin and to check the activity according to described in the international application WO 2004/005410.
  • the present invention also relates to a solid non-conductive support of electricity on which is grafted an organic film whose first unit covalently bonded to said non-conductive support of electricity is a derivative of an adhesion primer.
  • the solid non-conductive support of the electricity according to the present invention may optionally have a mask as previously defined.
  • the organic film comprises, in addition to the first unit covalently bonded to the non-conducting support of electricity derived from an adhesion primer, monomers of identical or different natures bonded to each other by radical reaction and optionally adhesion primer derivatives.
  • the organic film is an essentially polymeric film. More particularly, it may be in the form of a block polymeric film or a random copolymer film.
  • the non-conductive solid supports of the electricity, the adhesion primers and the monomers are as previously defined.
  • the solid support according to the invention may also comprise grafted grafts as previously described.
  • an organic film comprising nano-objects such as nanoparticles (NPs), nanocrystals (NCs) or nanotubes (NTs) typically corresponds to a film on the surface and up to the inside of which are present nano-objects (NBs).
  • nano-objects such as nanoparticles (NPs), nanocrystals (NCs) or nanotubes (NTs)
  • This embodiment is applicable to a support covered with an organic film and in particular to a support covered with an organic film covalently bonded to its surface, it will typically be a support obtained at the end of a method as previously described.
  • this embodiment corresponds in particular to a process for preparing a film organic composition comprising nano-objects from a solid support covered with an organic film, typically obtained by the process previously described, characterized in that the surface of the support is brought into contact with a suspension of at least one nanoparticles, object (NB) in a suspension solvent and in that the film and the nano-object have a physicochemical affinity.
  • NB nanoparticles, object
  • a nano-object corresponds to an object of nanometric size, generally its largest dimension is less than 1 ⁇ m and typically less than 25 nm. It may especially be a nanoparticle (NP), a nanocrystal (NC), a nanowire or a nanotube (NT) or a nanocolumn. It is obvious that the NBs in question here will advantageously have a size smaller than the thickness of the organic film present on the support, advantageously their largest dimension will not exceed 20%, generally 10% and typically 5%, of the thickness of the organic film.
  • the affinity is usually due to weak or strong interactions that develop between the NBs surface and the film.
  • weak type interactions there may be mentioned hydrogen bonds, ionic type bonds, complexation bonds, pi ("stacking") interactions, van der Waals bonds, hydrophobic bonds (or apolar bonds).
  • strong bonds include covalent bonds which can form spontaneously.
  • a simple NB consists of a single material, it is often an NP, an NC, a nanowire or an NP or nanocolumn, however, may have a variable constitution, including in the case of a non-uniformly doped NB in its entire volume.
  • a complex NB generally has different structural elements or parts whose composition is clearly distinct. It may, for example, be artificial assemblies of nanometric size having organic and inorganic structures or NP with ligands or NP multiple coatings.
  • a complex NB may consist of several simple NBs.
  • the NBs can in particular comprise at least one metal.
  • the metals can be chosen in particular from noble metals and transition metals, metals from groups
  • the invention is applicable to gold, platinum, palladium, rhodium, ruthenium, cobalt, nickel, silver, copper, titanium oxide, iron oxide, with iron-platinum, iron-palladium, gold-platinum and cobalt-platinum alloys.
  • the NBs can also consist only of the elements previously mentioned, it will be, in this case, NBs metal.
  • NBs may also include a semiconductor or an inorganic insulator. It can for example be compounds of formula AB with A an element whose oxidation state is +11 and B an element whose oxidation state is -II. Typically, A is selected from Mg, Ca, Sr, Ba, Zn, Cd, Hg, Sn, Pb and mixtures of these elements, and B is selected from O, S, Se, Te and mixtures of these elements.
  • semiconductors mention may also be made of semiconductors of formula CD with C being an element whose oxidation state is + III and D being an element whose oxidation state is -III.
  • C is selected from Al, Ga, In and mixtures of these elements
  • D is selected from N, P, As, Sb, Bi and mixtures of these elements.
  • Semiconductors of formula ECB 2 with E being an element whose oxidation state is +1, C being an element whose oxidation state is + III and B being an element whose oxidation state is -II, in which B and C are chosen as above, E is selected from Cu, Ag and Au, are also concerned by the invention.
  • simpler semiconductors such as Si or Ge, as well as their oxides and carbides, or insulators such as diamond.
  • the semiconductors may be in intrinsic or doped form. NBs can also consist only of the elements previously mentioned.
  • NBs may also include an element of organic nature.
  • these are usually specific molecular structures such as stabilizers or organic ligands or coating films.
  • For simple NB it will usually be carbon in a particular structural form such as a nanotube or a fullerene.
  • NBs can also consist only of the elements previously mentioned.
  • a NB is said to be "functionalized” when its surface comprises one or more BGi groups having an affinity for the "host film" which is the film present on the support.
  • BGi can thus correspond to a chemical function present on the surface, such as the OH functions that are present on the silica particles, as illustrated in the examples.
  • BGi can be present on one or only part of NB, for example in the case of an NP containing stabilizers, ligands or having a coating, BGi may be present on several organic stabilizers or on the coating.
  • a stabilizer corresponds to an organic molecule which binds to the surface of the heart of the nano-object and which keeps NB in the colloidal state, usefully in this field, the person skilled in the art can refer to Roucoux et al., Chem . Rev. 2002, 102, 3757-3778.
  • a functionalised nano-object typically has an inorganic core, or at least whose surface is inorganic, constituted by at least one metal and / or at least one semiconductor or an insulator such that defined above, which is bound at least one stabilizer having an organic group BGi.
  • a functionalised NB comprising an organic coating
  • such a functionalized NB may in particular be obtained by the process for preparing an organic film on the surface of a previously described support applied to a NB, ie corresponding to the heart that it is desirable to coat.
  • the nature of the core can be variable, both simple and complex and inorganic as organic, for further details it is useful to refer to what has been developed as well as examples that illustrate the application to different surfaces.
  • the organic film will be prepared so that it has a BGi group.
  • the stabilizers are chosen from amphiphilic molecules such as surfactants or polyoxanions, polymers such as PVP (polyvinylpyrolydone), PEG (polyethylene glycol), charged molecules of low molecular weight, generally less than 200 g. mol '1 , such as sodium citrate or sodium acetate, and finally chemical coordination ligands such as Lewis bases such as BINAP derivatives (2, 2'-bis (diphenylphosphino) -1, 1' - binaphthyl).
  • amphiphilic molecules such as surfactants or polyoxanions
  • polymers such as PVP (polyvinylpyrolydone), PEG (polyethylene glycol)
  • charged molecules of low molecular weight generally less than 200 g. mol '1 , such as sodium citrate or sodium acetate
  • chemical coordination ligands such as Lewis bases such as BINAP derivatives (2, 2'-bis (diphenylphosphino) -1,
  • the stabilizers that can be used in the context of the invention for functionalized NBs comprising a core composed of a metal and / or a semiconductor and / or an insulator, or the surface of which has such a composition are especially ligands of formula (III):
  • Y represents an atom or a group of atoms capable of bonding to a metal and / or a semiconductor compound and / or an insulator; SG represents a spacer group; BGi is as defined previously; p is 0 or 1.
  • Y will be chosen according to the heart of the NB which is used in the context of the process. Y can bind covalently, by complexation, chelation, or by electrostatic interaction on the surface of the heart.
  • the skilled person can refer in particular to the prior art and particularly Colloids and Colloid Assemblies, Frank Caruso (Ed.), 1. Ed. Dec 2003, Wiley-VCH, Weinheim or Templeton, A. C .; Wuelfing, W. P .; Murray, R.W., Monolayer-Protected Cluster Molecules. Ace. Chem. Res. 2000, 33 (1), 27 - 36.
  • Y may in particular be a thiol, a dithiol, a carbodithioate, dithiocarbamate, xanthate, when the core, or the surface of the core, corresponds to a metal such as gold, silver, copper, platinum, palladium or again when it or it corresponds to a type AB semiconductor such as CdSe, CdTe, ZnO, PbSe, PbS, CuInS 2 , CuInSe 2 or Cu (In, Ga) Se 2 .
  • a type AB semiconductor such as CdSe, CdTe, ZnO, PbSe, PbS, CuInS 2 , CuInSe 2 or Cu (In, Ga) Se 2 .
  • Y may especially correspond to a carboxylic acid, dicarboxylic acid, phosphonic, diphosphonic, sulphonic or hydroxamic acid, the acids may be in deprotonated form, as has been stated in the prior art and in particular in the international application WO 2004/097871.
  • a spacer group SG generally corresponds to a group which does not develop any interaction other than of steric nature, of hydrophilic or hydrophobic nature or of affinity with the heart. NB or the host organic film to which the process is applied, and which does not react significantly with them (not detectably).
  • the spacer may be a carbon chain lacking a heteroatom. It may, for example, be a chain of aliphatic nature, eg alkyl chain, preferably from 1 to 22, and typically from 6 to 16, carbon atoms, an aromatic chain, or a heterocyclic chain. like a polyether chain.
  • BG2 may be chosen from the groups previously listed for Y and the NBs will have a composition, or at least their surface, as previously listed in agreement with Y.
  • BG1 and BG3 then form a pair having an electron-type interaction which will typically be the seat of the affinity between the organic film and the functionalized NBs.
  • a support covered with a functionalized organic film so that it has both an organic group BG3 and a group BG2.
  • This embodiment is suitable when the NB comprises a coating or a stabilizer comprising groups of type BGi and when the surface of its core also comprises this type of group, the chemical functions present on the surface of the core, although both are susceptible to develop an interaction with the host movie, can of course be different.
  • BG2 and / or BG3 groups As a host organic film, functionalized with BG2 and / or BG3 groups, and as a coating film, functionalized with a BGi group, for NB core, it is advantageous to employ a film prepared according to the method previously exposed from a primer and a monomer different from the adhesion primer and radically polymerizable. It is recommended to use functionalisable films as they have been defined above, typically BG2 and BG3 may correspond to a GCF that includes the film. The presence of a monomer often easily derivatizable or having particular organic functions is suitable. As mentioned above, it is possible to modify the GCFs that a film has to access other GCFs.
  • This will be particularly acrylic acid.
  • this may comprise a precursor of the group BG1, BG2 or BG3, such a precursor may be transformed, when the user so decides, into a corresponding affinity group by carrying out a few steps, typically one or two, simple chemicals.
  • a host organic film it is of course possible to use a film functionalized with a graft.
  • a graft having a chelating property.
  • the group BG2 and / or BG3 advantageously corresponds to a GI as defined above, such a GI is a chelating or complexing structure.
  • the graft can be grafted according to the modalities presented above, it is possible in particular that it also comprises a link group LG as it has been defined.
  • films comprising molecules derived from cyclodextrins, prophyrin or callixarenes.
  • organic molecules or salts for example plob, such as lead nitrate, can be chelated or complexed.
  • Y will develop a weaker interaction with the heart of NB than the interaction that the surface of the heart could develop with the host film of the medium.
  • the interaction that could exist between the core of a complex NB and Y will advantageously be less strong than that which could exist between the heart of such NB and BG2.
  • the suspension solvent is a solvent which allows the formation of a suspension of NBs. They typically correspond to the solvents in which the NBs are prepared because they avoid or delay the aggregation of NBs.
  • the suspension solvent will advantageously be chosen from swelling solvents, as they have been defined above.
  • the suspension of NBs will preferably be homogenized before being used. He is, by For example, it is possible to subject the suspension to mechanical stirring, preferably vigorous, or to ultrasonic treatment.
  • the NBs concentration in the suspension and the duration of contact of the film with the suspension are variable and can be adapted according to the amount of NB that the user wishes to integrate into the film. Preliminary tests according to the affinity existing between the film and the NBs make it possible to easily determine reasonable operating conditions for the implementation of the method, usefully the user will refer to the examples. It is obvious that increasing the concentration of the suspension reduces the time required to integrate a given amount of NBs into the film. In the same way, the increase in the duration of the contact makes it possible to integrate a larger quantity of NBs for a given time.
  • a film comprising nanoparticles for a film of 200 to 300 nm, bringing into contact with an NPs suspension of Pt for 15 to 60 min makes it possible to obtain a film comprising nanoparticles.
  • a hydrophilic solvent such as water or a low molecular weight alcohol such as methanol or ethanol, or a mixture thereof.
  • the choice of a hydrophilic solvent makes it possible, for example, to produce a suspension of NPs of silica, gold or platinum stabilized with a stabilizer comprising a hydrophilic group, such as ammonium.
  • NBs having hydrophilic groups on their surface such as silica NPs.
  • the invention also makes it possible to produce film-coated supports comprising one or more coalescence zones from supports covered with organic films comprising NBs, the latter films being obtainable by the previously presented process.
  • the NBs incorporation method will be applied to NBs likely to coalesce under the action of a coalescing agent, and will comprise an additional step of exposure of at least one zone of the surface of the support, covered with the film comprising the NBs, with a coalescing agent.
  • the coalescence of NBs is generally defined as the disappearance of the boundary between two NBs in contact with each other, or between a NB and an object of larger size and similar composition, followed by a change of shape resulting in a reduction of the total area of the system.
  • the process is generally carried out by bringing into contact with the film comprising NBs, typically obtained according to the process described above, with the coalescing agent.
  • the method can of course be carried out on one or more zones of the support comprising the film by exposing said zone to the coalescing agent. This process can thus be realized in a localized way.
  • the coalescing agent may cause a modification of the support and any organic films and layers present on the support, a localized application of the agent may thus be preferable.
  • the NBs likely to undergo coalescence are, for example, simple NBs, it will generally be metallic NBs and in particular NCs or NPs of metals or metal alloys, or complex NBs such as functionalized NBs exhibiting metallic heart.
  • the coalescing agent may be a variation of a physical parameter or irradiation, when the method is applied to a particular area of the support the parameter will be modified only in this area.
  • Physical parameters that can be modified to coalesce NBs are known to those skilled in the art.
  • temperature modification or irradiation, photonic or electronic can be used.
  • a heat treatment at a temperature of between 250 and 500 ° C., and for example 250 ° to 350 ° C. for 2 to 5 minutes makes it possible to obtain the coalescence of platinum nanoparticles, such treatment being carried out on the whole of the surface of the support having a film comprising the nanoparticles leads to the formation of a homogeneous metal film.
  • Tests may be carried out to determine the minimum temperature for a given time according to the NBs and in particular according to their size as well as their composition.
  • a coherent infra-red source such as a CO2-type laser
  • the application of an electron beam for example using a microscope makes it possible to achieve localized coalescence of the NPs.
  • the present invention also relates to a solid electrically non-conductive support on which is grafted an organic film, comprising NBs, and particularly NPs, the first unit covalently bonded to said non-conductive support of electricity is a derivative of a primary adhesion.
  • the solid non-conductive support of the electricity according to the present invention may optionally have a mask as defined above, it may also comprise grafted molecules according to the previously described methods.
  • the organic film comprising NBs, and particularly NPs comprises, in addition to the first unit covalently bonded to the non-conductive support of electricity derived from an adhesion primer, monomers of identical natures or different, linked to each other by radical reaction and possibly derivatives of the adhesion primer.
  • the organic film is an essentially polymeric film. More particularly, it may be in the form of a block polymeric film or a random copolymer film. Solid non-conductive carriers of electricity, adhesion primers and the monomers are as previously defined.
  • NBs, and particularly NPs will be present in the outermost layers of the film.
  • electroplating solutions to form a metal coating, and in particular copper, on a support coated with an organic film obtained by the method described above.
  • the electrodeposition will be carried out on non-NBs organic films.
  • the skilled person will usefully refer to the international application WO 2007/034116 and in particular to the examples.
  • the method of electroplating on a support coated with an organic film can in particular be carried out by performing the following steps:
  • a so-called "cold-entry” step during which the surface of the support is brought into contact without electrical polarization with an electroplating bath, and preferably maintained in this state for a period of at least 5 seconds, preferably between 10 and 60 seconds, and preferably from about 10 to 30 seconds, a step of forming the metal coating during which said surface is polarized for a time sufficient to form said coating, a so-called “hot outlet” step, during which said surface is separated from the electrocoating bath while it is still under electrical polarization.
  • the present invention also relates to a method of metallizing an organic film prepared on the surface of a solid support comprising the steps of (a '') preparing, on the surface of a solid support, an organic film comprising nano -objects (NBs) according to a method as previously defined;
  • step (b '') contacting the film prepared in step (a '') with a solution containing at least one metal salt which can be reduced by said NBs.
  • a metal coating on a support coated with an organic film obtained by the method described above it is also possible to take advantage of the presence of NBs, and particularly NPs, within the organic film.
  • a solution comprising one or more metal salts that can be reduced by the NBs present in the organic film.
  • the support coated with an organic film comprising NBs will be directly immersed in a solution comprising one or more metal salts.
  • the exposure time of the support coated with the organic film comprising NBs to the metal salt solution is generally between thirty seconds and ten minutes.
  • the NBs concentration and the concentration of metal salts in the film can be adapted according to the thickness of the desired film.
  • NB it is possible to use in particular simple NBs, it will generally be NBs metal and especially NCs or NPs of metals such as gold or palladium, or metal alloys, or Complex NBs like functionalized NBs with a metallic core.
  • metal salts it is possible, for example, to choose from solutions of copper sulphate or nickel sulphate.
  • the present invention also relates to the use of a solution containing at least one solvent, at least one adhesion primer, optionally at least one monomer other than the adhesion primer and, optionally, at least one chemical initiator as defined above. to form, under non-electrochemical conditions and allowing the formation of at least one radical on the adhesion primer, an organic film on the surface of a solid support in contact with said solution.
  • the invention also relates to a kit for preparing an essentially polymeric organic film on the surface of a sample.
  • a kit for preparing an essentially polymeric organic film on the surface of a sample includes: in a first compartment, a solution containing at least one adhesion primer as defined above, optionally in a second compartment, a solution containing at least one radically polymerizable monomer different from the adhesion primer as previously defined, and optionally, in a third compartment, a solution containing at least one chemical polymerization initiator as defined above.
  • the kit according to the present invention may optionally, in addition, contain a compartment containing a suspension of at least one nano-object in a suspension solvent and / or a compartment containing a functionalization solution.
  • the first compartment contains not the solution containing at least one adhesion primer but a solution containing at least one precursor of an adhesion primer.
  • adheresion primer precursor it is necessary to understand a molecule separated from the primary by a single operating step and easy to implement.
  • the kit will possibly include at least one other compartment in which will be located at least one element necessary to develop the primary from its precursor
  • the kit may for example contain a solution of an aryleamine, precursor of the adhesion primer, and also a NaNU2 solution to allow by addition the formation of an aryl diazonium salt, primary adhesion.
  • a precursor makes it possible to avoid storing or transporting reactive chemical species.
  • the solvent may be contained in any of the solutions of the first and second compartments and optionally in the solution of the third or fourth compartment.
  • an identical or different solvent is contained in each of the solutions of the first and second compartments and optionally in the solution of the third or fourth compartment.
  • the solutions of the different compartments may of course contain different other identical or different agents such as stabilizing agents or surfactants.
  • the use of the kit proves to be simple since it suffices to place the sample whose surface is to be treated in contact with the mixture of solutions prepared extemporaneously by mixing the solutions of the different compartments, preferably with stirring and in particular under ultrasound .
  • the solution containing the i.e. monomer of the second compartment is placed under ultrasound before being mixed with the solution containing the adhesion primer prepared extemporaneously from a precursor or present in the solution of the first compartment.
  • the invention provides access to polymeric films having outstanding properties. he It should be noted first of all that the films have a particularly high degree of resistance, since after washing with a solvent in which the monomer is particularly soluble and in the presence of ultrasound, the thickness of the film does not vary significantly. . In addition, it is possible to control with remarkable efficiency the film thickness obtained by varying the experimental parameters such as the reaction time or the concentration of active species.
  • the composition of the films is also homogeneous and it is possible to control it with a high degree of precision, which gives access to both polymeric films of statistical type and of sequence type (also called block or alternating type).
  • the films are compliant, ie they have a homogeneous surface over the entire surface to which the process has been applied. This invention therefore allows access to a large number of functionalizations on a very large variety of surfaces with different monomers that can be associated with each other.
  • the advantages of the invention are manifold.
  • This method allows using a single method, simple and reproducible, access grafting conductive surfaces or not.
  • the implementation of this process does not require heavy investment in specific equipment such as potentiostats, expensive vacuum installations ...
  • the implementation of the process is simple and fast compared to other techniques today. known for grafting or coating surfaces.
  • This method does not require connection to an electrical circuit unlike electrochemistry and thus allows its application on difficult to connect surfaces such as nano objects.
  • this radical polymerization can be carried out in the presence of oxygen and does not involve special precautions during the synthesis.
  • the present invention can be used in an aqueous medium without any other apparatus than a container in which the reaction takes place.
  • the invention thus makes it possible to coat and functionalize, with great efficiency, a considerable number of surfaces of varied and hitherto undecorated or grafted nature such as a PTFE surface.
  • the fields of application are very numerous and such a method is for example applicable in biology, in particular for biocompatibility procedures (stent coating), for functionalization and in particular the protection of surfaces, such as metals.
  • the functionalization can be localized thanks to the use of mask. It is thus possible to precisely coat different areas of the same surface by protecting other areas with one or more masks. This type of procedure is easily implemented because easily removable organic masks can be used, it may include simple deposits made using ink impregnated pens or coating with a fatty substance.
  • the implementation of the method according to the invention is also part of a non-polluting approach since it can be carried out in an aqueous medium and that it produces little waste, one of the reaction products may be especially dinitrogen.
  • FIG. 1 shows the IR spectrum of a gold plate treated according to a variant of the process of the present invention with a solution whose diazonium salt was prepared in situ from p-benzylamine.
  • Figure 2 shows the IR spectrum of a gold plate treated according to a variant of the process of the present invention ie with a solution whose diazonium salt was prepared in situ from p-phenyldiamine.
  • FIG. 3 the IR spectrum of a gold plate treated according to a variant of the process of the present invention, ie with a diazonium solution, after 5, 10 and 15 minutes of exposure of the blade (respectively (a) , (b) and (c)).
  • Figure 4 shows the IR spectrum of a nickel plate treated according to an alternative of the process of the present invention with a solution whose diazonium salt was prepared in situ from p-benzylamine.
  • Figure 5 shows the IR spectrum of a steel blade (AISI 316L) processed according to a variant of the process of the present invention with a solution whose diazonium salt was prepared in situ from p-benzylamine.
  • AISI 316L steel blade
  • FIG. 6 represents an AFM image of a diamond surface covered with a primer film (FIG. 6a) and a profilometric curve (length X (nm) / height Z (A)) of this surface indicated by a double arrow on the AFM image ( Figure 6b).
  • Figure 7 provides the schematic representation of a sequential film (Figure 7a) and a statistical film (Figure 7b) prepared according to the present invention.
  • Figure 8 provides a schematic representation of the grafting methods of the state of the art ( Figure 8a) and the method according to the present invention ( Figure 8b).
  • Figure 9 shows the IR spectrum of a gold plate treated according to an alternative of the process of the present invention i.e. with a solution of which the diazonium salt was prepared in situ and using a monomer.
  • FIG. 10 shows, for a gold strip treated in accordance with the present invention, with a primer and a monomer, on the one hand, the IR spectrum of said gold plate treated at different exposure times (FIG. 10a). and, on the other hand, the IR spectrum of said processed gold plate as a function of the amount of iron filings ( Figure 10b).
  • Figure 11 shows the XPS spectroscopy (X-ray photoelectron spectroscopy) analyzes of a conductive carbon felt ( Figure 11a) and same carbon felt on which is grafted an organic film prepared according to the process of the present invention ie from a diazonium salt created in situ and acrylic acid and in the presence of iron filings (PAA for polymer of acrylic acid) ( Figure Hb).
  • XPS spectroscopy X-ray photoelectron spectroscopy
  • Figure 12 shows the IR spectrum of a gold plate treated according to the method of the present invention to form a sequential film.
  • Figure 13 shows the IR spectrum of a gold plate processed according to the method of the present invention to form a random film.
  • Figure 14 shows the IR spectrum of a gold plate treated according to the process of the present invention to form a film from a monomer insoluble in the reaction solvent.
  • FIG. 15 shows the IR spectrum of a glass slide treated according to the method of the present invention with a primer and a monomer.
  • FIG. 16 shows a photograph of carbon nanotubes (FIG. 16a) and a photograph of carbon nanotubes after a treatment according to the invention with a primer and a monomer (FIG. 16b).
  • Figure 17 shows the IR spectrum of a PTFE slide processed according to the process of the present invention with a primer and a monomer.
  • FIG. 18 shows the IR spectra obtained for a gold plate (FIG. 18a) and a titanium plate (FIG. 18b) treated identically and according to the method of the present invention, ie from of 2-hydroxyethylmethacrylate and a diazonium salt prepared in situ in the presence of iron filings.
  • Figure 19 shows the photograph of a drop of water on a blank glass slide ( Figure 19a) and the photograph of a drop of water on the same glass slide coated with p-butyl methacrylate (p-BuMA) according to to the process according to the invention ( Figure 19b).
  • Figure 19a shows the photograph of a drop of water on a blank glass slide
  • Figure 19b shows the photograph of a drop of water on the same glass slide coated with p-butyl methacrylate (p-BuMA) according to to the process according to the invention
  • Figure 20 shows the IR / AFM mapping obtained for gold plates coated with a commercial ink mask after treatment by the process in the presence of hydroxymethylmethacrylate (Figure 20a) or acrylic acid ( Figure 20b) and removal of the mask.
  • FIG. 21 shows the IR / AFM mapping obtained for a gold plate covered with a thiol mask after treatment by the process in the presence of acrylic acid and removal of the mask.
  • Figure 22 shows the IR / AFM mapping obtained for a gold plate covered with a thiol mask after treatment by the process in the presence of hydroxymethylmethacrylate and removal of the mask with different patterns ( Figure 22a and Figure 22b).
  • Figure 23 shows the IRRAS spectrum of a gold plate covered with a film comprising PHEMA and a cyclodextrin derivative.
  • Figure 24 shows the IRRAS spectrum of a gold plate covered with a film comprising PHEMA and a calixarene derivative.
  • Figure 25 shows the XPS, Ci 3 spectra
  • FIG. 26 shows an XPS (global) spectrum of a film comprising PAA, grafted onto a gold plate, before incorporation of the Pt nanoparticles.
  • FIG. 27 shows an XPS (global) spectrum of a film comprising PAA, grafted onto a gold plate, after incorporation of the Pt nanoparticles.
  • FIG. 28 shows an XPS (global) spectrum of a film comprising PAA, grafted onto carbon nanotubes, after incorporation of the Pt nanoparticles.
  • the following examples were carried out in a glass vessel. Unless otherwise specified, they were made under normal conditions of temperature and pressure (about 25 ° C. under about 1 atm) in ambient air. Unless otherwise stated, the reagents employed were directly obtained commercially without further purification. The gold plates used had a surface of 1 cm 2 . No precautions were taken concerning the composition of the atmosphere and the solutions were not degassed. When the reaction time is not specified, it was an exposure of the surface to be treated for 1 to 15 minutes to the reagent solution.
  • the first relates to films prepared using an adhesion primer, the second films prepared using an adhesion primer and of a monomer, the third the functionalisable films, the fourth the films containing nano-objects.
  • Example 1-1 Preparation of a film on a gold plate from a para-benzyl amine diazonium salt, prepared in situ in the presence of iron filings 4 ml of a solution of para benzylamine
  • Example 1-2 Preparation of a film on a gold plate from a diazonium salt derived from p-phenyldiamine prepared in situ in the presence of iron filings
  • a solution of diazonium salt in water was prepared by adding to 4 ml of a 0.1 M solution (4.10 -4 moles) p-4-aminobenzylamine in HCl (0.5 M). ml of a solution of 0.1 M NaNO2 (4.10 "4 moles) with stirring. To this solution was added a gold leaf.
  • the solution was then placed in non-electrochemical conditions allowing the formation of radicals on the adhesion primer by the addition of 200 mg of iron filings.
  • the plate was then extracted from the reaction medium and rinsed immediately with water and then with acetone and dimethylformamide (DMF) under the action of ultrasound and finally dried under a stream of argon.
  • DMF dimethylformamide
  • the exposure time of the sample to the reaction medium has an influence on the thickness of the film obtained. Exposure times of 5, 10 and 15 minutes were tested, it appears that prolonged exposure increases the thickness of the film. Indeed, the increase in the intensity of the adsorption bands of poly-p-4-aminobenzylamine 1504 cm -1 , 1605 cm -1 and 1656 cm -1 translates an increase in the thickness of the film over time.
  • Example 1-4 Preparation of a film on a gold plate from commercial p-nitrophenyldiazonium in the presence of iron filings
  • Example 1-2 The experiment was carried out according to the protocol described in Example 1-2 using commercial p-nitrophenyldiazonium (Aldrich®) solubilized at 0.05M in a solution of HCl (0.5M). The gold plate was then immersed in the solution for about 15 minutes. The plate was then rinsed with water and acetone, sonicated in DMF and then in water before being dried. As previously, the XPS spectrometric analyzes confirmed the presence of the expected film whose thickness increases with the reaction time.
  • Aldrich® commercial p-nitrophenyldiazonium
  • Example 1-5 Preparation of a film on a gold plate from a diazonium salt created in situ in the presence of steel wool
  • Example 1-1 The procedure is identical to that of Example 1-1.
  • the iron filings have been replaced by approximately 5-10 mg of steel wool fibers (supplier CASTORAMA®) successively fine (0), extra fine (00) and super fine (000), which makes it possible not to have solid iron residues in the solution.
  • Example 1-6 Preparation of a film on a gold plate from a diazonium salt created in situ in basic medium The procedure is identical to that of Example 1-1. To the iron filings, 0.3 ml of a 2.5% sodium hydroxide solution was substituted. 10 ⁇ 3 M to allow a slight rise in pH above 4.
  • the XPS and IR analyzes confirm the presence of the expected film whose thickness increases with the reaction time.
  • Example 1-7 Preparation of a film on a gold plate from a diazonium salt created in situ initiated by an irradiated PVDF membrane.
  • Example 1-1 The procedure is identical to that of Example 1-1. To the iron filings was substituted an irradiated PVDF membrane (2 cm, thickness 9 ⁇ m, electron irradiation dose: 100 kGy). IR analyzes confirmed the presence of the expected film whose thickness increased with the reaction time.
  • Example 1-8 Preparation of a film on a glass slide from a diazonium salt prepared in situ in the presence of iron filings
  • Example 1-9 Preparation of a film on a nickel plate from a diazonium salt prepared in situ in the presence of iron filings
  • the protocol is identical to that presented in Example 1-1, a slide of Nickel was used in this case with a reaction temperature of 40 ° C.
  • the IR spectrum obtained (FIG. 4) confirms the presence of the expected film whose thickness increases with the reaction time.
  • Example 1-10 Preparation of a film on a steel strip (AISI 316L) from a diazonium salt prepared in situ in the presence of iron filings
  • Example 1-11 Preparation of a film on diamond from a diazonium salt prepared in situ in the presence of iron filings
  • the protocol is identical to that presented in Example 1-1, a piece of diamond a been used in this case.
  • An AFM image ( Figure 6) confirms the presence of the expected film whose thickness increases with the reaction time, the profilometric analysis shows the presence of the film on the surface.
  • II Adhesion primer and monomer
  • Example II-1 Preparation of a film on a gold plate from a diazonium salt prepared in situ and 2-hydroxyethyl methacrylate (HEMA) in the presence of iron filings
  • Table 3 presented below combines a set of thickness values obtained for the same reagents by varying their concentrations, the exposure time or the amount of filings.
  • the process was applied to a gold plate, placed in the presence of a solution containing an adhesion primer, 4-aminophenyldiazonium chloride, and a monomer, HEMA, under non-electrochemical conditions allowing the formation of a radical entity from the adhesion primer.
  • This choice was motivated in particular by the presence of adsorption characteristics at 1726, 1454 and 1166 nm of poly - HEMA.
  • a solution of adhesion primer in water was prepared by adding to 4 ml of a 0.1 M solution (4.10 -4 mol) of p-phenylenediamine in HCl (0.5 M), 4 ml of a solution of NaNO 2 at 0.1 M (4.10 -4 mol) with stirring. To this solution was added 1 ml (8.24 mmol) of HEMA), as well as a gold slide. 2-1. influence of the reaction time
  • the solution was then placed under non-electrochemical conditions allowing the formation of radicals on the adhesion primer by the addition of 200 mg of iron filings.
  • the plate was then extracted from the reaction medium and rinsed immediately with water and then with acetone and dimethylformamide (DMF) under the action of ultrasound and finally dried under a stream of argon.
  • DMF dimethylformamide
  • the exposure time of the sample to the reaction medium has an influence on the thickness of the film obtained.
  • the increase in the intensity of the HEMA adsorption bands at 1726, 1454 and 1166 nm reflects an increase in the thickness of the film over time.
  • the thickness of the films was measured using a profilometer: it varies from 12 nm to 200 nm for an exposure time ranging from 1 to 15 min.
  • the amount of iron filings present in the reaction medium has an influence on the thickness of the film obtained.
  • a minimum amount of filings is necessary to generate enough radicals in the reaction medium and to obtain a graft film of detectable thickness in IR. Beyond a certain maximum value of filings, the thickness variations of the film obtained are negligible.
  • Example II-3 Preparation of a film on a gold plate from commercial p-nitrophenyldiazonium and HEMA. in the presence of iron filings
  • the experiment was carried out according to the protocol described in Example II-2 using commercial p-nitrophenyldiazonium (Aldrich®) solubilized at 0.05 M in a solution of HCl (0.5 M ).
  • Aldrich® commercial p-nitrophenyldiazonium
  • the gold plate was then immersed in the solution for about 15 minutes.
  • the plate was then rinsed with water and acetone, sonicated in DMF and then in water before being dried.
  • Example II-4 Preparation of a film on a gold plate from a diazonium salt created in situ and HEMA. in basic medium The procedure is identical to that of Example II-2. To the iron filings were substituted 0.3 ml of a solution of soda at 2.5. 10 ⁇ 3 M to allow a slight rise in pH above 4. The XPS and IR analyzes confirm the presence of the expected film whose thickness increases with the reaction time.
  • Example II-5 Preparation of a film on a conductive carbon felt from a diazonium salt created in situ and acrylic acid (AA) in the presence of iron filings
  • Example II-2 The example was carried out according to the methods described in Example II-2, the monomer used in this case was acrylic acid (1 ml) and the sample was made of carbon felt.
  • the XPS analysis as shown by the spectrum of FIG. 11, confirms the presence of the expected film.
  • Example II-6 Preparation of a sequential film on a gold plate from a diazonium prepared in situ, HEMA and AA in the presence of iron filings
  • Example II-2 a plate was prepared and cleaned according to the modalities of Example II-2. A new solution of the same diazonium salt was then prepared and 1 ml of acrylic acid and then 200 mg of the iron filings were added to it. The plate prepared beforehand according to Example II-2 was then introduced into the reaction medium for a variable time at the end of which it was cleaned and dried as described above.
  • Figure 12 shows the IR spectrum obtained for such a plate after 15 minutes of reaction.
  • the characteristic bands of the PAA (acrylic acid polymer) at 1590 and 1253 nm appear on the spectrum of Example 2.
  • Example II-7 Preparation of a statistical film on a gold plate from a diazonium prepared in situ, HEMA. and AA in the presence of iron filings
  • the IR spectrum obtained is shown in FIG. 13: it confirms the presence of the expected statistical film consisting in particular of the two monomers.
  • Example II-8 Preparation of a film on a gold plate from a diazonium salt prepared in situ and 4-vinylpyridine (4VP) in the presence of iron filings
  • a solution of diazonium salt prepared according to Example II-2 containing a gold plate was added 200 mg of iron filings and then a dispersion of 1 ml of 4-vinylpyridine in 10 ml of water, prepared by ultrasonic treatment. After a variable reaction time, the blade is then cleaned and dried in the manner described above.
  • the IR spectrum obtained for the plate is shown in FIG. 14.
  • the characteristic bands at 1602, 1554 and 1419 nm validate the presence of the expected film.
  • Example II-9 Preparation of a film on a glass slide from a diazonium salt prepared in situ and HEMA. in the presence of iron filings
  • the protocol is identical to that shown in Example II-2, a glass slide having been used in this case.
  • the IR spectrum shown in FIG. 15 confirms the presence of the expected film whose thickness increases with the reaction time.
  • Example 11-10 Preparation of a film on carbon nanotubes from a diazonium salt prepared in situ and HEMA. in the presence of iron filings
  • Example II-2 To a solution of diazonium salt prepared as in Example II-2 was added 200 mg of iron filings and 1 ml of HEMA. To this solution was then added 100 mg of carbon nanotubes in the form of carpets. The carpet, after reaction, was cleaned according to the protocol described in Example 2 before being dried.
  • FIG. 16 The photographs obtained by scanning electron microscopy (SEM), shown in FIG. 16, correspond to front nanotubes (FIG. 16a) and after (FIG. 16b) treatment.
  • Example 11-11 Preparation of a film on a surface of PTFE (Teflon®) from a diazonium salt prepared in situ and HEMA. in the presence of iron filings
  • the spectrometric and IR analyzes confirm the presence of the expected film whose thickness increases with the reaction time.
  • Example 11-12 application of the method to different samples
  • Example 11-14 Preparation of a film on a glass plate from a diazonium salt prepared in situ and butyl methacrylate in the presence of iron filings
  • Example 11-15 Preparation of a film on a gold plate exhibiting a commercial ink mask from a diazonium salt prepared in situ and hydroxymethylmetacrylate (HEMA) or acrylic acid (AA) in the presence of iron filings
  • HEMA hydroxymethylmetacrylate
  • AA acrylic acid
  • Example II-2 for HEMA and 5 for AA.
  • the blade Prior to its introduction into the reaction medium, the blade was coated with a mask: different patterns were made on the gold leaf with a black ink pen (Staedtler®-lumocolor®) .
  • FIG. 20 The different maps (IR / AFM) obtained are illustrated in FIG. 20.
  • IR infrared spectroscopy
  • C O bands for each of the polymers
  • AFM Atomic Force Microscopy
  • Example 11-16 Preparation of a film on a gold plate having a thiol mask from a diazonium salt prepared in situ and acrylic acid (AA) in the presence of iron filings
  • Example 11-15 The protocol that was used is identical to that of Example 11-15. Prior to its introduction into the reaction medium, a drop of an ethanolic solution of long-chain (C18) thiol was deposited on the slide, the slide was treated after evaporation of the ethanol.
  • Example 11-15 After the treatment the slide was cleaned and analyzed as in Example 11-15.
  • FIGS. 21a and 21b respectively represent a three-dimensional view (it is a measurement in transmitance, also, the raised areas correspond to ungrafted areas) and a plane view of the blade (the clear zone corresponding to the ungrafted zone). It can be seen in these figures that the areas which were covered by the mask do not have graft film.
  • Example 11-17 Preparation of a film on a gold surface having a micro-printed thiol mask from a diazonium salt prepared in situ and hydroxymethylmetacrylate (HEMA) in the presence of iron filings
  • Example 11-15 The protocol that was used is identical to that of Example 11-15. Prior to its introduction into the reaction medium the slide is covered with a thiol mask using a PDMS buffer having micrometric patterns and previously impregnated with an ethanolic solution of long-chain thiol (C18). The slide was treated after evaporation of the ethanol.
  • Example 11-15 After the treatment the slide was cleaned and analyzed as in Example 11-15.
  • FIG. 22a shows that the grafted surface corresponds to the inverse of the triangular micrometric patterns on the buffer and in FIG. 22b shows micrometric patterns corresponding to lines (this is the measurement in FIG. transmissivity, too, the raised areas correspond to the ungrafted areas).
  • Example II Preparation of a film on a gold plate from a diazonium salt created in situ initiated by a non-porous PVDF membrane irradiated with electrons and in the presence of acetonitrile (ACN).
  • ACN acetonitrile
  • Example II Preparation of a film on a gold plate from a diazonium salt created in situ initiated by a nanoporous PVDF membrane reirradiated to electrons and in the presence of acetonitrile (ACN).
  • ACN acetonitrile
  • Example II Preparation of a film on a gold plate from an in situ created diazonium salt initiated by an electron-irradiated PVDF membrane in the presence of acrylic acid (AA).
  • Non-porous electron-irradiated PVDF (2 cm, thickness 9 ⁇ m, electron irradiation dose: 100 kGy).
  • a plate of gold was then introduced into the reaction medium for 15 min always under an inert atmosphere (Ar).
  • the plate was then rinsed with water and acetone, ultrasonic treatment was applied before the plate was dried.
  • IR analyzes confirmed the presence of the expected film whose thickness increased with the reaction time.
  • Example II Preparation of a film on a gold plate from a diazonium salt created in situ initiated by a nanoporous PVDF membrane reirradiated to electrons in the presence of acrylic acid (AA).
  • AA acrylic acid
  • Pore size 50 nm) reirradiated to electrons (2 cm, thickness 9 ⁇ m, electron irradiation dose: 100 kGy).
  • a gold plate was then introduced into the reaction medium for 15 min always under an inert atmosphere (Ar).
  • the plate was then rinsed water with acetone, sonicated before drying.
  • Example II Preparation of a film on a gold plate from an in situ created diazonium salt initiated by an electron-irradiated PVDF membrane in the presence of acetonitrile (ACN) and acrylic acid (AA).
  • ACN acetonitrile
  • AA acrylic acid
  • Example II Preparation of a film on a gold plate from a diazonium salt created in situ initiated by a nanoporous PVDF membrane reirradiated to electrons, in the presence of acetonitrile (ACN) and acid acrylic (AA).
  • ACN acetonitrile
  • AA acid acrylic
  • Pore size 50 nm) reirradiated to electrons (2 cm, thickness 9 ⁇ m, electron irradiation dose: 100 kGy).
  • Example II Preparation of a film on a gold plate from commercial p-nitrophenyldiazonium and 2-hydroxyethyl methacrylate (HEMA) in the presence of ferrocene.
  • HEMA 2-hydroxyethyl methacrylate
  • IR analyzes confirmed the presence of the expected film whose thickness increases with the reaction time.
  • the specific bands of poly-HEMA at 1726, 1454 and 1166 cm- 1 are visible on the IR spectrum of a plate after treatment.
  • Example II Preparation of a film on the surface of multiwall carbon nanotubes (MWCNTs) from commercial p-nitrophenyldiazonium and butyl methacrylate (BUMA) in the presence of ferrocene.
  • a solution of 0.04 mol of ferrocene in 5 ml of BUMA (3.10 "3 M) is added a solution previously sonicated 10.2 mg of MWCNTs in 8 ml of dimethylformamide (DMF) This mixture was stirred for 3 hours.
  • DMF dimethylformamide
  • Example II Preparation of a film on the surface of a carpet of multiwall carbon nanotubes (MWCNTs) from commercial p-nitrophenyldiazonium and 2-hydroxyethylmethacrylate (HEMA) in the presence of ferrocene.
  • MWCNTs multiwall carbon nanotubes
  • HEMA 2-hydroxyethylmethacrylate
  • Example III-1 - film comprising PHEMA and grafts derived from CD on a gold plate
  • the carboxylic acid function of PaCD (10 mg) was then activated by forming an ester activated with N, N'-diisopropylcarbodiimide (DIC) (6 eq.) In DMF (5 mg). ml) with stirring for 6 hours in the presence of catalytic amounts (0.05 eq) of dimethylamino pyridine (DMAP).
  • DMAP dimethylamino pyridine
  • PHEMA poly (2-hydroxyethyl) methacrylate
  • Example III-2 Film Comprising PAA and CD-Derived Grafts, with a Linker Group, on a Gold Slide
  • PaCD was prepared according to Example III-1.
  • a propanol arm was added to the PaCD to form a graft with a linking group (LG).
  • reaction mixture was stirred for 72 hours at room temperature and the slide is extracted, rinsed with DMF and acetone before being dried.
  • Example III-3 Film with PHEMA and grafts derived from calixarene on a gold plate
  • the calixarene derivative shown below this one was based on literature (Bulletin of the Korean Chemical Society (2001), 22 (3), 321-324).
  • PHEMA poly (2-hydroxyethyl) methacrylate
  • Example III-4 Film Containing Amino Polybenzyl and Porphyrin-Derived Grafts on a Gold Plate
  • a prophyrin whose carboxylic acid function was activated by formation of an activated ester was employed.
  • the activated ester was formed by reacting tetrakis (bezoic acid) -4, 4 ', 4'',4''' - (Porphyrin-5, 10, 15, 20-tetrayl) (10 mg; "5 mol) with N, N'-diisopropylcarbodiimide (6 eq) in DMF in the presence of a catalytic amount of DMAP (0.05 eq).
  • a 2 cm 2 gold surface plate having a 0.6 nm thick polybenzyl amine film and prepared according to the methods of Example 1-1 was placed in a flask containing the activated porphyrin. .
  • the reaction medium was stirred for 72 h at room temperature and the slide was extracted, rinsed with DMF and acetone before being dried.
  • XPS analysis confirmed the presence of porphyrin on the film.
  • the Ni 3 spectrum shown in Figure 25b, is composed of two peaks, one centered on 399.5 eV, is typical of the nitrogen included in an aromatic ring and corresponds to that of porphyrin nitrogens.
  • Example IV-I - Incorporation of platinum nanoparticles in a film comprising polyacrylic acid grafted onto Au An organic copolymer film derived from acryclic acid (AA) and a diazonium salt prepared in situ, grafted onto a plate of gold and comprising platinum nanoparticles has been prepared.
  • AA acryclic acid
  • the colloidal suspension was prepared at 20 ° C. To 300 mg of HEA-16-C1 dissolved in 5 ml of ultrapure water was added 3.6 mg of sodium borohydride (NaBH 4 ). This solution was then rapidly added with vigorous stirring to 5 ml of ultrapure water containing 12 mg of platinum tetrachloride (PtCl 4 ). Reduction of Pt (IV) in Pt (O) is characterized by a change in color from pale yellow to black / brown. The suspension was left an hour under mechanical agitation before use. This suspension is stable for several weeks.
  • the gold strip covered with the organic film was dipped in a 0.5 M sodium hydroxide solution for 5 minutes and then dried without additional rinsing. This step has made it possible to convert the carboxylic acid groups, the affinity group precursor, PAA into carboxylate groups, which have an affinity for the particles. 1 ml of colloidal suspension of Pt (O) was then deposited on the gold plate coated with the film. After 15 minutes, the slide was rinsed (Water / Ethanol / acetone) before being dried and analyzed by XPS.
  • FIG. 27 corresponds to an XPS spectrum of the film after the integration of the particles, compared to FIG. 26, which corresponds to the film before the incorporation of the particles.
  • Example IV-2 Incorporation of gold nanoparticles into a film comprising polyacrylic acid grafted onto steel (AISI 316L)
  • a copolymeric organic film derived from acryclic acid (AA) and a diazonium salt prepared in situ, grafted onto a steel plate (AISI 316L) and comprising gold nanoparticles was prepared.
  • the colloidal suspension was prepared at 20 ° C. To 300 mg of HEA-16-C1 dissolved in 5 ml of ultrapure water was added 3.6 mg of sodium borohydride (NaBH 4 ). This solution was then added rapidly with vigorous stirring to 5 ml of ultrapure water containing 12 mg of gold salt (AuHCl 4 ). The reduction of Au (IV) to Au (O) is characterized by a change in color from pale yellow to brick red. The suspension was left for one hour with mechanical stirring before use. This suspension is stable for several weeks. 2-3.
  • the steel strip (AISI 316L) covered with the organic film was immersed in a 0.5 M sodium hydroxide solution for 5 minutes and then dried without additional rinsing. This step has made it possible to convert the carboxylic acid groups, the affinity group precursor, PAA into carboxylate groups, which have an affinity for the particles. 1 ml of colloidal suspension of Au (O) was then deposited on the steel plate (AISI 316L) coated with the film. After 15 minutes, the blade has been rinsed
  • Example IV-3 Incorporation of platinum nanoparticles into a film comprising polyacrylic acid grafted onto carbon nanotubes
  • An organic copolymer film derived from acyclic acid (AA) and a diazonium salt prepared in situ, grafted onto a carpet of carbon nanotubes and comprising platinum nanoparticles was prepared.
  • Example II-2 To a solution of diazonium salt prepared as in Example II-2 was added 200 mg of iron filings and 1 ml of Acrylic Acid. To this solution was then added 100 mg of carbon nanotubes in the form of carpets. The carpet, after reaction, was cleaned according to the protocol described in Example IV-2 before being dried.
  • the nanotube mat covered with the organic film was immersed in a 0.5 M sodium hydroxide solution for 5 minutes and then dried without additional rinsing. This step made it possible to convert the carboxylic acid groups, affinity group precursor, PAA into groups carboxylates, which have an affinity for the particles. 1 ml of colloidal suspension of Pt (O) was then deposited on the carpet of nanotubes coated with the film. After 15 minutes, the nanotube mat was rinsed (Water / Ethanol / acetone) before being dried and analyzed by XPS.
  • Example IV-4 Incorporation of platinum nanoparticles in an Au-grafted polybenzyl amine film
  • the gold strip covered with the organic film was dipped in a 0.5 M sodium hydroxide solution for 5 minutes and then dried without additional rinsing. This step made it possible to convert the ammonium groups, affinity group precursors, into amino groups which have an affinity for the particles. 1 ml of colloidal suspension of Pt (O) was then deposited on the gold plate coated with the film. After 15 minutes, the slide was rinsed (Water / Ethanol / acetone) before being dried and analyzed by XPS.
  • Example IV-5 Incorporation of silica nanoparticles into a film comprising Au-grafted polyacrylic acid
  • silica particles (provided by DEGUSA®) of small size (about 12 nm in diameter) non-porous and finely divided were employed. Each particle is substantially spherical and has a surface area of about 200 m .g- 1 and contains about 1 mmol.g- 1 of silanol groups.
  • the colloidal solution of silica particle was obtained by mixing 10 mg of silica in 10 ml of distilled water.
  • Example IV-6 Incorporation of platinum nanoparticles into a film comprising polyacrylic acid grafted onto glass and plastic
  • Example IV-7 Coalescence of the nanoparticles present in the films
  • EXAMPLE IV-8 Metallization of the film by chemical reduction of a solution of metal salts using the nanoparticles present in the films
  • a metallization bath was prepared with two solutions, the first containing 3 g of copper sulfate, 14 g of sodium and potassium tartrate and 4 g of sodium hydroxide in 100 ml of distilled water.
  • the second solution is an aqueous solution of formaldehyde 37.02% by weight.
  • the two solutions were mixed in a ratio of 10: 1 and 20 ml of the mixture were taken to immerse the supports, glass or gold, covered with organic film comprising nanoparticles of Au or Pt, obtained according to the examples. IV-I, IV-4 and IV-6 for 5 min.
  • Example IV-9 - Metallization of the polymer film by chemical reduction of a solution of metal salts using the nanoparticles of paladium present in the films
  • a colloidal suspension of palladium was then prepared by ultrasonic exposure for 5 minutes of a solution of 0.3 g of the previously obtained powder in 200 ml of toluene.
  • the suspension is stable for several months.
  • the incorporation of the particles is carried out by dipping the plastic film of polyethylene or polypropylene coated with a film grafted in the suspension obtained in Example 9-2, the film is then rinsed with toluene and then dried under an argon stream.
  • the metallization is carried out according to the same procedure as in the example example IV-8. A metal film is then visible to the naked eye.

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PCT/FR2007/052556 2006-12-19 2007-12-19 Procédé de préparation d'un film organique à la surface d'un support solide dans des conditions non-électrochimiques, support solide ainsi obtenu et kit de préparation WO2008078052A2 (fr)

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EP07871969A EP2121814B1 (fr) 2006-12-19 2007-12-19 Procédé de préparation d'un film organique à la surface d'un support solide dans des conditions non-électrochimiques, support solide ainsi obtenu et kit de préparation
AT07871969T ATE509977T1 (de) 2006-12-19 2007-12-19 Verfahren zur herstellung eines organischen films an der oberfläche eines festen substrats unter nicht-elektrochemischen bedingungen, auf diese weise hergestelltes festsubstrat und herstellungsset
CN2007800504618A CN101595170B (zh) 2006-12-19 2007-12-19 在非电化学条件下在固体支撑物表面制备有机膜的方法，由此得到的固体支撑物和制备成套器具
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FR2943930A1 (fr) * 2009-04-02 2010-10-08 Commissariat Energie Atomique Procede pour modifier l'energie de surface d'un solide
WO2010125190A1 (fr) * 2009-04-30 2010-11-04 Commissariat à l'énergie atomique et aux énergies alternatives Procédé de préparation d'un film organique à la surface d'un support solide avec traitement oxydant
WO2011073363A1 (fr) 2009-12-18 2011-06-23 Commissariat à l'énergie atomique et aux énergies alternatives Membrane échangeuse de cations à sélectivité améliorée, son procédé de préparation et ses utilisations.
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EP2402403A1 (fr) 2010-07-02 2012-01-04 Institut Français de Recherche pour l'Exploitation de la Mer (IFREMER) Exopolysaccharides pour la prévention et la lutte contre la formation de biofilms
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FR2910010A1 (fr) 2008-06-20
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FR2910010B1 (fr) 2009-03-06
AU2007337938A2 (en) 2009-09-03
AU2007337938A1 (en) 2008-07-03
JP5588682B2 (ja) 2014-09-10
US20080145706A1 (en) 2008-06-19
AU2007337938B2 (en) 2013-09-05
WO2008078052A3 (fr) 2008-09-18
CN101595170A (zh) 2009-12-02
JP2010513647A (ja) 2010-04-30
IL199417A (en) 2014-06-30
ATE509977T1 (de) 2011-06-15
US8709542B2 (en) 2014-04-29
CN101595170B (zh) 2013-01-23
EP2121814A2 (fr) 2009-11-25

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